[go: up one dir, main page]

EP1260747A1 - Kunststoffschlauch für kraftstoff - Google Patents

Kunststoffschlauch für kraftstoff Download PDF

Info

Publication number
EP1260747A1
EP1260747A1 EP01908232A EP01908232A EP1260747A1 EP 1260747 A1 EP1260747 A1 EP 1260747A1 EP 01908232 A EP01908232 A EP 01908232A EP 01908232 A EP01908232 A EP 01908232A EP 1260747 A1 EP1260747 A1 EP 1260747A1
Authority
EP
European Patent Office
Prior art keywords
modified
resin hose
fuel
inner tube
fluoroplastic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01908232A
Other languages
English (en)
French (fr)
Inventor
Masaki c/o Toyoda Gosei Co. Ltd. KOIKE
Kenichi c/o Toyoda Gosei Co. Ltd. MITSUI
Shinichi c/o Toyoda Gosei Co. Ltd. BITO
Daisuke c/o Toyoda Gosei Co. Ltd. TSUTSUMI
Mitsutaka c/o Toyoda Gosei Co. Ltd. KONDO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyoda Gosei Co Ltd
Original Assignee
Toyoda Gosei Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyoda Gosei Co Ltd filed Critical Toyoda Gosei Co Ltd
Publication of EP1260747A1 publication Critical patent/EP1260747A1/de
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/06—Hoses, i.e. flexible pipes made of rubber or flexible plastics with homogeneous wall
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/11—Hoses, i.e. flexible pipes made of rubber or flexible plastics with corrugated wall
    • F16L11/111—Hoses, i.e. flexible pipes made of rubber or flexible plastics with corrugated wall with homogeneous wall
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/12—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting
    • F16L11/127—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting electrically conducting
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • Y10T428/1393—Multilayer [continuous layer]

Definitions

  • the present invention relates to a resin hose for fuel. More particularly, it relates to a resin hose for fuel of a plural-layer structure excellent in gasoline impermeability and superior also in productivity.
  • the resin hose for fuel is generally required to have complex properties including fuel resistance, gasohol resistance (resistance to gasoline containing alcohol), fuel impermeability, and moisture impermeability.
  • gasohol resistance resistance to gasoline containing alcohol
  • fuel impermeability resistance to gasoline containing alcohol
  • moisture impermeability Recently, in particular, regulations about fuel permeation is becoming stricter from the viewpoint of environmental protection in several nations including the United States. It is said that, in future, the fuel permeation quantity per vehicle need to be controlled under 1/4 of the present quantity. Accordingly, in resin hoses for fuel of a single layer formed of polyamide such as nylon 11 or nylon 12 excellent in fuel oil resistance and superior in relative flexibility, it is predicted hard to satisfy the requirement of fuel impermeability.
  • the inner peripheral wall in which the fuel in the resin hose for fuel flows is required to be conductive in order to discharge (destaticize) the static electricity.
  • a metal junction 22 coated with fluororubber 20 when a metal junction 22 coated with fluororubber 20 is force-fitted, it was found hard to maintain a sufficient sealing performance for a long period. In particular, such tendency was significant in the configuration having hemispherical stopping bumps 22a, 22a at one or two positions as shown in the illustrated example, instead of the factory type of leading end metal junction (nipple) 22 of metal pipe 24.
  • the inventors hit upon an idea of resin hose for fuel of the following configuration in the process of strenuous efforts in development for solving these problems.
  • a resin hose for fuel in a plural-layer structure comprising a main body layer made of aliphatic polyamide, and an inner tube layer made of fluoroplastic disposed at the inner side of the main body layer
  • the aliphatic polyamide (aliphatic PA) and fluoroplastic are respectively modified aliphatic PA and modified fluoroplastic, and the characteristics of the both satisfy the requirements of difference of melting point (DSC method) of 60°C or less, and difference of modulus of flexural elasticity (ASTM D 790) of 1500 MPa or less or 500 MPa or less
  • DSC method difference of melting point
  • ASTM D 790 difference of modulus of flexural elasticity
  • the modified fluoroplastic is modified by incorporating a functional group capable of reactive-bonding or associating with a functional group of the aliphatic PA including modified or unmodified, so that the chemical adhesion between the main body layer and inner tube layer may be assured easily.
  • a functional group capable of reactive-bonding or associating with a functional group of the aliphatic PA including modified or unmodified so that the chemical adhesion between the main body layer and inner tube layer may be assured easily.
  • fluoroplastics modified by maleic acid and/or epoxy, or incorporated with a carbonate group and/or a halide carboxylate group are preferably used.
  • the modified aliphatic PA is modified by incorporating a functional group capable of reactive-bonding or associating with a functional group of the fluoroplastic including modified or unmodified, so that it is expected to improve the chemical adhesion further.
  • the modified aliphatic group the material increased in the content of amino group (including imino group) is used preferably.
  • the modified aliphatic PA is made of modified nylon 11 and/or modified nylon 12, or mainly made thereof, and the modified fluoroplastic is made of modified ethylene-tetrafluoroethylene copolymer (modified ETFE) or mainly made thereof, so that the characteristic requirements of both layers can be satisfied easily, and the fuel permeability can be suppressed at the same time.
  • modified ETFE modified ethylene-tetrafluoroethylene copolymer
  • the inner tube layer usually contains conductive filler as modified fluoroplastic resin, and a conductive path is formed continuously in the longitudinal direction in the inner peripheral wall of the inner tube layer, and the inner peripheral wall side of each inner tube layer has a conductivity of surface resistivity (ASTM D 991) of 10 10 ohms or less, so that the electric charge by flow of fuel can be discharged favorably.
  • conductive filler as modified fluoroplastic resin
  • a conductive path is formed continuously in the longitudinal direction in the inner peripheral wall of the inner tube layer, and the inner peripheral wall side of each inner tube layer has a conductivity of surface resistivity (ASTM D 991) of 10 10 ohms or less, so that the electric charge by flow of fuel can be discharged favorably.
  • the extrusion speed is preferred to be 5 m/min or more.
  • the extrusion speed it is expected to increase the adhesion strength between the main body layer and inner tube layer. That is, the residence time in the extrusion head is shortened, and it is estimated that the decrease rate of the bonding function group amount is suppressed.
  • connection structure of the resin hose of plural layers of the present invention is to solve the above problems by the following configuration.
  • the fluoroplastic for forming the inner tube layer is a modified fluoroplastic by incorporating a polar group, and it is expected to increase the adhesion of the inner tube against the fluororubber coat film on the metal junction surface. That is, in the prior art, the adhesion and sealing performance of the fluororubber coat film and PA (nylon 11, 12, etc.) could be assured somewhat, and its reasons are estimated as follows.
  • the fluororubber polymer (FKM) itself has a higher SP value (dissolution parameter: square root of cohesive energy density) as compared with the fluoroplastic.
  • the portion for forming the coat film is not made of FKM alone, but contains various subsidiary materials of high SP value (polar materials), and the SP value of the coat film is expected to be higher than that of the FKM itself.
  • polar materials for example, vulcanizers (polyamine, polyol, organic peroxide, etc.), vulcanization aids (phosphonium salt, etc.), and metal oxides (MgO, CaO, etc.) are all polar materials of high SP value, and further the carbon black contains chemical active groups such as quinone group and hydroquinone group on the surface. Generally, the chemical formation property is established in the SP value.
  • FKM fluororubber
  • PTFE fluoroplastic
  • nylon 8 nylon 8
  • the first value is cited from "Basic synthetic rubber lecture, New series” ed. by Kimura, (Taiseisha, July 25, 1988, Appendix), and the latter two values are cited from "Adhesion Handbook, second edition” ed. by Japan Adhesion Society (November 10, 1980, p. 110) respectively.
  • Fluoroplastics represented by PTFE are small in SP values by nature as quoted above, but when modified by incorporating polar groups to form modified fluoroplastics, the SP value of the inner tube layer becomes similar to that of the fluororubber coat film, and hence it is estimated that the adhesion between the inner tube layer and fluororubber coat film is increased.
  • the inner tube layer is preferred to be formed of a modified fluoroplastic by incorporating a functional group containing carbonyl groups such as a carbonate group and/or halide carboxylate group (a halogenated carboxylic acid group).
  • a functional group containing carbonyl groups such as a carbonate group and/or halide carboxylate group (a halogenated carboxylic acid group).
  • the fluororubber coat film is preferable to be formed of fluororubber blend of polyol vulcanization system or amine vulcanization system. Chemicals used in these vulcanization systems have active hydrogen, and are expected to have a stronger reaction adhesion (chemical bond) with the modified fluoroplastic for forming the inner tube layer.
  • connection structure of the present invention has an effect of securely blocking permeation of fuel through the metal junction when applied in the fuel resin hose using aliphatic PA as the material for the main body layer adjacent to the outside of the inner tube layer.
  • connection structure of the resin hose of plural layers having the above configuration is formed by the following connection method.
  • the inner tube layer is formed of modified fluoroplastic incorporating a functional group containing carbonyl groups, such as a carbonate group and/or a halide carboxylate group
  • the coat film is formed of a fluororubber blend of polyol vulcanization system or amine vulcanization system, and therefore along with force-fitting of the metal junction with the fluororubber coat film in semi-vulcanized state, the reaction bonding (vulcanization adhesion) of the inner tube layer and rubber coat film becomes stronger.
  • a resin hose for fuel 12 of the present invention basically has a structure of plural layers comprising a main body layer 14 made of aliphatic polyamide, and an inner tuber layer 16 made of fluoroplastic disposed at the inside of the main body layer 14.
  • the illustrated example is a two-layer structure of a main body layer 14 and the inner tuber layer 16, but it may be also composed of three to six layers comprising a protector layer and other functional layers at the outside of the resin hose for fuel 12.
  • the resin hose for fuel 12 can be enhanced in flexibility by forming bellows B by blow molding after co-extrusion as shown in Fig. 5.
  • the fuel includes gasoline, alcohol-added gasoline (gasohol), light oil, LPG and other fuels for vehicles.
  • the resin hose for fuel 12 of the present invention is suited to impermeability of fuel such as gasoline and alcohol-added gasoline as shown in embodiments below.
  • the reason of using aliphatic PA as the main body layer 14 is that the aliphatic PA is a resin for general purpose, and is excellent in resistance to fuel and gasohol.
  • lactam polymer diamine-dicarboxylic acid condensate, amino acid polymer, and their copolymers and blends may be used.
  • Specific examples include nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, and nylon 12.
  • nylon 11 and/or nylon 12 it is particularly preferred to use nylon 11 and/or nylon 12 as main ingredient.
  • Nylon 11 and/or nylon 12 are excellent in flexibility (the modulus of flexural elasticity is below half) as compared with each nylon 6 or nylon 66 for general purpose, and are also low in fuel permeability (about 1/4 or less in permeability), and these characteristics are particularly required in the resin hose for fuel.
  • the modulus of flexural elasticity of nylon is nylon 6: 2.8 x 10 3 MPa, nylon 66: 2.8 x 10 3 MPa, nylon 11: 1.2 x 10 3 MPa, and nylon 12: 1.1 x 10 3 MPa, and the moisture absorption (saturated humidity) is nylon 6: 9.5 wt.%, nylon 66: 8.5 wt.%. nylon 11: 1.9 wt.%, and nylon 12: 1.5 wt.% (See T. Mita (ed.): "Maruzen Polymer Dictionary", September 20, 1994, Maruzen, Table 1, p. 987).
  • a fluoroplastic is used in the inner tube layer 16 because it is far excellent in various characteristics such as fuel resistance and fuel impermeability as compared with the aliphatic PA.
  • fluoroplastics examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (CTFE), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-polychlorotrifluoroethylene copolymer (ECTFE), hexafluoropropylene-tetrafluoroethylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinylether copolymer (PFA), other copolymers, various graft polymers, and blends.
  • ETFE is particularly preferred.
  • the melting point is low, the forming property is excellent, and mechanical properties such as impact resistance (Izod impact value) and tensile strength are also superior.
  • the melting point (DSC method) of each fluoroplastic is PTFE: 327°C, ETFE: 270°C, the impact strength (ASTM D 256A) is PTFE: 160 J/m, ETFE: not broken, the modulus of flexural elasticity (ASTM D 790) is PTFE: 549 MPa, and ETFE: 1373 MPa.
  • ETFE is copolymerized with ethylene, a vinyl compound having a functional group can be copolymerized at the same time, and polymer modification mentioned below is easier.
  • various characteristic aids and additives can be added.
  • Such examples include reinforcing agent, filler and pigment.
  • one or both of the aliphatic polyamide (aliphatic PA) and the fluoroplastic are modified aliphatic PA and modified fluoroplastic, respectively, and the characteristics of the two satisfy the requirements of difference of melting points (DSC method) of about 60°C or less (preferably about 40°C or less, more preferably about 20°C or less), and difference of moduli of flexural elasticity (ASTM D 790) of about 1500 MPa or less or about 500 MPa or less, and therefore the main body layer 14 and the inner tube layer 16 are directly adhered to each other by co-extrusion.
  • DSC method difference of melting points
  • ASTM D 790 difference of moduli of flexural elasticity
  • the difference of melting points is too large, it is hard to co-extrude the main body layer and the inner tube layer, and a sufficient adhesion strength can be hardly maintained between the two, or the layer thickness is likely to disperse when forming.
  • the difference of moduli of flexural elasticity is too large, it is hard to maintain a sufficient adhesion strength (for example, 30 N/cm or more of peeling adhesion strength conforming to JIS K 6854; same hereinafter) between the main body layer and the inner tube layer at the time of flexural fatigue.
  • a sufficient adhesion strength for example, 30 N/cm or more of peeling adhesion strength conforming to JIS K 6854; same hereinafter
  • the difference of the moduli of flexural elasticity (ASTM D 790) between the main body layer 14 and the inner tube layer 16 is preferred to be smaller, for example, about 500 MPa or less, preferably about 300 MPa or less, or more preferably about 200 MPa or less.
  • the combination of the aliphatic polyamide and the modified fluoroplastic for example, when the modified fluoroplastic (modified by maleic acid) with 1). melting point: 210°C and 2) modulus of flexural elasticity: 900 MPa is used, nylon 12 (melting point: 175°C, modulus of flexural elasticity: 700 MPa) or nylon 11 (melting point: 180°C, modulus of flexural elasticity: 500 MPa) may be combined. Physical properties of nylon 11 and nylon 12 refer to the value of composition containing plasticizers.
  • the modified fluoroplastic is a kind of resin modified in a range not to disturb the original characteristics of the fluoroplastic, by copolymerizing a comonomer (usually vinyl compound) containing functional group or multifunctional comonomer at the time of synthesizing each fluoroplastic (polymer), or by incorporating a functional group capable of reactive-bonding or associating (hydrogen bonding) with a functional group of the modified aliphatic PA in the main chain or the side chain of the polymer by graft coplymerization or substitution reaction of trace amount.
  • a comonomer usually vinyl compound
  • multifunctional comonomer at the time of synthesizing each fluoroplastic (polymer)
  • a functional group capable of reactive-bonding or associating (hydrogen bonding) with a functional group of the modified aliphatic PA in the main chain or the side chain of the polymer by graft coplymerization or substitution reaction of trace amount.
  • the function groups possessed by the modified aliphatic polyamide include amino groups (imino group), mercapto group, methylol group, isocyanate group, carboxyl group, hydroxyl group, halogen group, acid anhydride, aldehyde group, epoxy group.
  • the amino group (imino group) is preferred. This is because the amino group (imino group) is initially contained in the aliphatic polyamide itself, and it is easy to modify the aliphatic polyamide.
  • the functional groups having reactivity with the amino group include carbonate groups, halide carboxylate groups, carboxyl group, acid anhydride, epoxy group, hydroxyl group, chloromethyl group, isocyanate group, amino group, and aldehyde group.
  • modified fluoroplastic modified by maleic acids (maleic acid anhydride; acid anhydride) and/or modified epoxy, or a compound incorporating carbonate group and/or halide carboxylate group may be preferably used.
  • R is a hydrogen atom or an organic group (for example, alkyl group with C1 to C20, alkyl group with C2 to C20 having ether bond, etc.
  • the halide carboxylate group is expressed in the formula - COY [Y is a halogen element], and specific examples include -COF, -COCl, etc.
  • the modified aliphatic PA is modified by copolymerizing traces of comonomer containing functional group or multifunctional one at the time of polymerization of each aliphatic PA (polymer), or by incorporating a functional group capable of reactive-bonding or associating (hydrogen bonding) with a functional group of the modified fluoroplastic in the main chain or the side chain of the polymer by graft copolymerization or substitution reaction.
  • the functional group is preferred to be incorporated in the terminal of polymer main chain, and the functional group is preferred to be amino groups (imino group) as stated above.
  • the amino groups may be easily increased by ⁇ -lactam or ⁇ -amino acid of a small number of carbon atoms (for example, C6 or less), diamine, triamine, etc.
  • a functional group shown in other examples of fluoroplastic may be incorporated.
  • a functional group shown in other examples of fluoroplastic may be incorporated.
  • by copolymerizing hydroxyl amine, tricarboxylic acid, hydroxyl carboxylic acid, or epichlorohydrine incorporation of functional group (hydroxyl group, carboxyl group, epoxy group, etc.) may be expected.
  • the resin material for forming the main body layer and/or inner tube layer is a functional group incorporated resin, if the residence time in the extrusion head becomes long, it is estimated that the functional group is dissociated to impede the adhesion (see Fig. 7 of the result of the test example describe below).
  • the specification of the resin hose for fuel is, supposing the overall outside diameter to be 6 to 10 mm in a double structure, main body layer: modified nylon 12, inner tube layer: modified ETFE, overall wall thickness: 0.8 to 1.2 mm, main body layer: 0.6 to 1 mm, and inner tube layer: 0.2 to 0.4 mm. If the inner tube layer is too thin, notable improvement of fuel impermeability is not expected, or if it is too thick, the overall rigidity of the hose (tube) is too high, and the flexibility of the fuel tube is sacrificed.
  • the resin hose for fuel usually has a conductivity of surface resistivity of 10 10 ohms or less at the inner peripheral wall side 16a of the inner tube layer 16 in order to destaticize the electric charge (discharge the static electricity).
  • This surface resistivity is a value not to cause an electric charge in an object when grounded, and it is generally achieved by a material with the volume resistivity of 10 10 ⁇ cm or less.
  • a conductive filler may be contained, for example, as the modified fluoroplastic, so that the volume resistivity may be 10 10 ⁇ cm or less.
  • conductive filler examples include carbon black, graphite, stainless steel, other metal materials of high conductivity such as Au, Ag, Cu, Ni, Pd, and Si, and metal oxides of these metal materials.
  • the resin hose for fuel having destaticizable conductivity in the inner peripheral wall side 16a of the inner tube layer 16 can be obtained, so that the fuel resin hoses can be manufactured at high productivity.
  • a conductive path 18 may be formed continuously in the longitudinal direction in contact with the inner wall 16a side of the inner tube layer 16 as shown in Fig. 3, or by burying in the inner wall 16a side of the inner tube layer 16 as shown in Fig. 4. In the illustrated examples, it is formed in stripes from the viewpoint of saving the material, but it may be also formed in a band.
  • the material for forming the conductive path 18 may be any fluoroplastic that can be co-extruded with the inner tube layer 16 and fused thermally, for example, a material containing the conductive filler on the ETFE when the inner tube layer 16 is formed of modified ETFE.
  • a conductive paint may be applied by dipping to form at least on the inner wall of the fuel resin hose of double structure.
  • the material for forming the conductive path 18, if the material being co-extrudable or adherable with the inner tube layer 16, may be a conductive resin having conductivity in the resin itself without containing conductive filler.
  • a conductive resin various materials may be used, including straight chain conjugate high polymer, surface conjugate high polymer, electric charge transfer complex type high polymer, radical ion type high polymer, other high polymer containing metal complex, and others.
  • conductive ETFE and conductive nylon may be used.
  • the layer thickness of the conductive path 18 is preferred to be as small as possible, as far as the conductivity may be provided, from the viewpoint of saving the materials.
  • the modulus of flexural elasticity of the conductive path 18 is preferred to be closer to the modulus of flexural elasticity of the inner tube layer 16 rather than the modulus of flexural elasticity of the main body layer 14, from the viewpoint of lessening of the stress applied to the interface of the inner tube layer 16 and the conductive path 18 when bending or force-fitting the fuel hose 12.
  • the resin hose for fuel of the present invention is a resin hose for fuel composed of plural layers comprising, as mentioned above, a main body layer made of aliphatic polyamide, and an inner tube layer made of fluoroplastic disposed at the inside of the main body layer, in which one or both of the aliphatic polyamide (aliphatic PA) and fluoroplastic are respectively modified aliphatic PA and modified fluoroplastic, and the characteristics of the both satisfy the requirements of difference in melting point (DSC method) of 60°C or less, and difference in modulus of flexural elasticity (ASTM D 790) of 1500 MPa or less or 500 MPa or less, the main body layer and inner tube layer are directly adhered to each other by co-extrusion, and therefore the fuel impermeability is excellent, and it can be manufactured at high productivity.
  • DSC method difference in melting point
  • ASTM D 790 difference in modulus of flexural elasticity
  • a destaticizable resin hose for fuel can be manufactured without any extra conductive treatment in addition to the forming of the inner tube layer.
  • connection structure of the present invention is a connection structure for force-fitting a resin hose for fuel (resin hose of plural layers) into a metal junction having a fluororubber coat film.
  • a metal pipe 24 has hemispherical sectional stopping bumps 22a, 22a in the illustrated example.
  • the material of the metal pipe 24 is optional, including iron, aluminum, copper, or their alloys.
  • stainless steel austenitic steel
  • the stopping bumps 22a, 22a are formed by cutting of cast or forged pieces in the case of metal joints, but are formed by bulge processing when forming as part of pipe at the leading end of metal piping (fuel piping). At this time, the bulging amount is a maximum diameter of 8.5 to 9.5 mm, for example, when the pipe diameter is 8 mm.
  • a fluororubber coat film 20 is formed of a solution type paint: a fluororubber polymer (FKM) composition incorporating various additive being dissolved in a solvent, or formed of a latex (emulsion) type paint: an FKM composition being emulsified in water.
  • the solution type is easier to form a uniform coat film (the film thickness can be adjusted easily by adjusting the viscosity by the solvent of immersion and application).
  • the dispersion medium (solvent) can be evaporated quickly, so that the coat film may be solidified in a short time.
  • the coat film thickness depends on the size of dispersion particles.
  • the coating method including immersion, spraying, brushing, etc. is optional. It is easier to obtain a uniform film thickness in the immersion coating.
  • the FKM is not particularly limited, and includes vinylidene fluoride compound (230°C, -17°C), fluorosilicone compound (185°C, -67°C), tetrafluoroethylene-propylene compound (230°C, -0°C), fluorophosphagen compound (175°C, - 68°C), tetrafluoroethylene-perfluorovinylether compound (250°C, 0°C), and others.
  • Figures in parentheses are heat resistance (temperature of continuous use in air) and cold resistance (TR-10) cited from Table 2-13 (p. 49) of "ABC of New Rubber Technology" edited by Tokai Branch of the Society of Rubber Industry, Japan. As for TR-10, refer to the item of "low temperature elasticity restoration test" of JIS K 6261.
  • the vinylidene fluoride compound when applied in a fuel resin hose, is preferred because the balance of heat resistance and cold resistance is excellent as shown in parentheses.
  • the vinylidene fluoride compound is classified into the vinylidene fluoride-hexafluoropropylene binary copolymer type, and vinylidene fluoride-hexafluoropropylene ternary copolymer type, and the latter is superior in heat resistance, oil resistance, and chemical resistance, but is more expensive as compared with the former type (see the cited reference).
  • the type of the rubber composition for forming the fluororubber coat film 16 is optional, including peroxide vulcanization system, amine vulcanization system, and polyol vulcanization system, but by using the blend containing the vulcanizer having active hydrogen such as amine-polyol vulcanization system, reactive adhesion (chemical bond) with the modified fluoroplastic for forming the inner tube layer 16 mentioned below is expected.
  • the FKM paint of polyol vulcanization system is prepared by dissolving the composition of the following blending formulation in an organic solvent (methyl ethyl ketone: MEK).
  • MEK methyl ethyl ketone
  • the paint viscosity at this time is 70 to 100 cPs (type B viscometer No. 2 rotor 100 rpm).
  • Blend formulation of FKM paint FKM master batch 100 parts (vinylidene fluoride-hexafluoropropylene binary system) MT black 13 parts
  • the film thickness (dry) of fluororubber coat film is usually 10 to 100 ⁇ m, preferably 20 to 50 ⁇ m. If too thin, the action as the coat film is hardly obtained (mainly the shock absorbing action between the metal junction and the inner tube layer, and gap generation compensation action), and if too thick, further improvement of the coat film action is not expected (action is saturated), and it is hard to force-fit the metal junction into the resin hose.
  • the fluororubber coat film 20 and metal junction 22 usually, it is hard to obtain a sufficient tightness (adhesion) directly. Accordingly, as pretreatment before applying fluororubber paint, it is preferred to coat with a primer.
  • a silane coupling agent is used preferably (for example, Chemlock 607 of Lord).
  • the coat film thickness of the primer is preferred to be as thin as possible as far as a sufficient adhesion is maintained between the fluororubber coat film and the metal junction, so that the degree of freedom of film thickness of the fluororubber coat film 20 is increased.
  • the primer coating method is optional, same as in the case of fluororubber coat film, and includes immersion, spraying, brushing, etc.
  • the fluororubber coat film formed by applying the fluororubber paint may be vulcanized, but in semi-vulcanized state, the metal junction may be force-fitted into the resin hose described below.
  • the semi-vulcanized state refers to an non-vulcanized state as much as possible in a range not causing problems in force-fitting work when force-fitting the metal junction into the resin hose or sealing performance after force-fitting.
  • the vulcanization curve by cure-meter it should be in a range of T 40 to T 70 , preferably T 50 to T 60 .
  • the conditions of heat treatment is, for example, 30 to 60°C x 90 to 30 min, preferably 40°C x 60 min. If the heating temperature is too high, the progress cannot be stopped in semi-vulcanized state of FKM, and when coated with primer, it is hard to supply heat necessary for primer. If the heating temperature is too low, to the contrary, it takes too much time to reach semi-vulcanized state (the productivity of connection structure is lowered).
  • the fuel resin hose 12 in the connection structure of the present embodiment is usually, as mentioned above, a plural-layer structure comprising the main body layer 14 made of aliphatic PA or the like, and the inner tube layer 16 made of fluoroplastic disposed inside of the main body layer 14.
  • the illustrated example shows a two-layer structure of the main body layer 14 and the inner tube layer 16, but it may be also composed of three to six layers comprising a barrier layer, an adhesive layer, a protector layer and other functional layers at the outside of the fuel resin hose 12, or between the main body layer 14 and the inner tube layer 16.
  • the resin hose for fuel 12A can be enhanced in flexibility by forming bellows B by blow molding after co-extrusion.
  • the corona discharge process requires a simple apparatus as compared with the plasma discharge process.
  • the corona discharge process is executed as follows.
  • the end of the plural-layer resin hose is expanded (flared), and is brought closer to the electrodes in reduced pressure atmosphere.
  • the condition at this time is output: 800 W, voltage between electrodes: 12 kV, distance between electrode and hose end: 20 mm, and discharge time: 0.5 to 20 sec.
  • the peeling strength (JIS K 6718) between the main body layer and the inner tube layer was 20 N/cm or more in embodiment 1 and 40 N/cm or more in embodiment 2, and favorable interlayer adhesion was recorded.
  • Modified nylon 12 (1) (amino end groups: 1.64/10000 monomer units, plasticizer: BSBA 5%): Melting point: 175°C, modulus of flexural elasticity: 700 MPa.
  • Modified nylon 12 (2) (amino end groups: 2.26/10000 monomer units, plasticizer: BSBA 5%): Melting point: 170°C, modulus of flexural elasticity: 400 MPa.
  • Modified ETFE (modified by maleic acid) (1): Melting point: 210°C, modulus of flexural elasticity: 900 MPa.
  • Modified ETFE (modified by carbonate) (2): Melting point: 200°C, modulus of flexural elasticity: 1400 MPa.
  • Non-modified ETFE (3) Melting point: 220°C, modulus of flexural elasticity: 600 MPa.
  • the specified fluororubber paint was applied and heated in the condition of 40°C x 60 min, and a semi-vulcanized rubber coat film (film thickness: about 30 ⁇ m) 20 was formed, and a metal pipe 24 with the rubber coated metal junction 22 was prepared (see Fig. 2).
  • the metal junction was force-fitted into the resin hose of embodiments 1 and 2 and comparative example 2, and after letting stand at room temperature for 24 hours, the samples were loaded by the air heating test in the condition of 130°C x 96 h, and the proof pressure test was conducted by using the fuel hose proof pressure testing machine (own make) in the conditions of:

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Laminated Bodies (AREA)
EP01908232A 2000-03-03 2001-03-02 Kunststoffschlauch für kraftstoff Withdrawn EP1260747A1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2000058662 2000-03-03
JP2000058662 2000-03-03
JP2000299167 2000-09-29
JP2000299167 2000-09-29
PCT/JP2001/001603 WO2001065161A1 (en) 2000-03-03 2001-03-02 Resin hose for fuel

Publications (1)

Publication Number Publication Date
EP1260747A1 true EP1260747A1 (de) 2002-11-27

Family

ID=26586722

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01908232A Withdrawn EP1260747A1 (de) 2000-03-03 2001-03-02 Kunststoffschlauch für kraftstoff

Country Status (5)

Country Link
US (1) US20030099799A1 (de)
EP (1) EP1260747A1 (de)
CN (1) CN1226544C (de)
AU (1) AU2001236043A1 (de)
WO (1) WO2001065161A1 (de)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1450092A1 (de) * 2003-02-24 2004-08-25 MANIFATTURA TUBI GOMMA S.p.A. Flüssigkeitsführendes Rohr und Verfahren zu seiner Herstellung
EP1484346A1 (de) * 2003-06-06 2004-12-08 Atofina Verfahren zur Pfropfung von Fluorpolymeren und Schichtverbundmaterial daraus
FR2856403A1 (fr) * 2003-06-06 2004-12-24 Atofina Procede de greffage de polymere fluore et structures multicouches comprenant ce polymere greffe
EP1580474A1 (de) * 2004-03-25 2005-09-28 MANIFATTURA TUBI GOMMA S.p.A. Mehrschichtiger, flexibler Schlauch
WO2006097678A1 (en) * 2005-03-14 2006-09-21 Wellstream International Limited Pipe fitting
WO2007021782A1 (en) * 2005-08-12 2007-02-22 E. I. Du Pont De Nemours And Company Multilayered pipes
WO2007083041A3 (fr) * 2006-01-20 2007-10-18 Arkema France Tuyau flexible en polyamide pour l’air comprime
US7472723B2 (en) 2004-03-17 2009-01-06 Manifattura Tubi Gomma S.P.A. Tube for conveying fluids and method for its production
EP1897685A4 (de) * 2005-06-14 2010-10-27 Asahi Glass Co Ltd Mehrschichtiges fluorharzlaminat
WO2012017265A1 (en) * 2010-08-02 2012-02-09 Intertechnique Tube with protrusions for inflatable harness of breathing mask
WO2012028948A3 (en) * 2010-09-03 2012-04-26 Aerazur S.A. Thermoplastic hoses for airborne vehicles
EP2101095A3 (de) * 2008-03-12 2013-07-17 Rehau AG + Co Wellschlauch aus Kunststoffmaterial zur Ummantelung von wenigstens einem Abgassensor-Kabel
US8627713B2 (en) 2008-09-08 2014-01-14 Arkema France Method for predetermining the fatigue life of polymer composition
EP2918885A1 (de) * 2014-03-14 2015-09-16 Veritas Ag Schlauchleitung für ein fluid
CN106051330A (zh) * 2016-07-21 2016-10-26 中山市庆谊金属制品企业有限公司 一种新型水管
WO2020120523A1 (de) 2018-12-12 2020-06-18 Ems-Patent Ag Mehrschicht-kraftstoffleitung
EP3882316A1 (de) * 2020-03-20 2021-09-22 ContiTech Techno-Chemie GmbH Umlageschlauch mit einem fkm-coating

Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4209595B2 (ja) * 2000-04-24 2009-01-14 旭硝子株式会社 燃料用ホース
US20050217746A1 (en) * 2002-04-09 2005-10-06 Mitsuboshi Corporation Limited Multi-layer tube
JP2004169851A (ja) * 2002-11-21 2004-06-17 Sanoh Industrial Co Ltd 多層チューブ
BRPI0409131A (pt) * 2003-04-08 2006-03-28 Omega Flex Inc conjunto de tubulação
JP4120476B2 (ja) * 2003-05-27 2008-07-16 宇部興産株式会社 コルゲートチューブ
US7241817B2 (en) * 2003-06-06 2007-07-10 Arkema France Process for grafting a fluoropolymer and multilayer structures comprising this grafted polymer
JP4678303B2 (ja) * 2003-11-14 2011-04-27 ダイキン工業株式会社 流動体輸送管、半導体製造ラインシステム及び液晶パネル製造ラインシステム
EP1704998B1 (de) 2004-01-13 2011-04-20 Asahi Glass Company, Limited Mehrschichtiges laminat
BRPI0510373B1 (pt) * 2004-04-27 2016-07-05 Kuraray Co "mangueira em multicamadas, que atua em alta temperatura, pelo menos igual e superior a 50ºc, para o transporte de uma substância química líquida e/ou gasosa".
WO2005121042A2 (en) * 2004-05-06 2005-12-22 Integral Technologies, Inc. Low cost conductive pipe manufactured from conductive loaded resin-based materials
WO2006017283A1 (en) * 2004-07-12 2006-02-16 Integral Technologies, Inc. Low cost vehicle fuel system components manufactured from conductive loaded resin-based materials
US20060070677A1 (en) * 2004-09-28 2006-04-06 Tokai Rubber Industries, Ltd. Hose with sealing layer, direct-connect assembly including the same, and method of manufacturing the same
JP2006118669A (ja) * 2004-10-25 2006-05-11 Sanoh Industrial Co Ltd 樹脂チューブ
EP1757443A1 (de) 2005-08-25 2007-02-28 Solvay Advanced Polymers, L.L.C. Structure ameliorée multicouche en polymère
FR2879281B1 (fr) * 2004-12-13 2007-02-16 Nobel Plastiques Soc Par Actio Tube fluoropolymere/evoh/pa modifie
US7806213B2 (en) 2004-12-17 2010-10-05 Tokai Rubber Industries, Ltd. Piping structure for transporting a fuel
JP2006194432A (ja) 2004-12-17 2006-07-27 Tokai Rubber Ind Ltd 燃料輸送用の配管部材
CN100402911C (zh) * 2004-12-17 2008-07-16 东海橡胶工业株式会社 用于输送燃料的管道组件
JP2007196522A (ja) * 2006-01-26 2007-08-09 Kurashiki Kako Co Ltd 燃料チューブ
FR2906862A1 (fr) * 2006-10-10 2008-04-11 Nobel Plastiques Soc Par Actio Canalisation ppa/fluoropolymere
FR2906863B1 (fr) * 2006-10-10 2008-12-05 Nobel Plastiques Soc Par Actio Canalisation hydraulique ppa/thermoplastique
JP4450018B2 (ja) * 2007-06-28 2010-04-14 日産自動車株式会社 多層ホース
US8127445B2 (en) * 2008-04-03 2012-03-06 E. I. Du Pont De Nemours And Company Method for integrating heat transfer members, and an LED device
US20100034504A1 (en) * 2008-08-08 2010-02-11 E.I. Du Pont De Nemours And Company Melt Processible Semicrystalline Fluoropolymer Comprising Repeating Units Arising from Tetrafluoroethylene and a Hydrocarbon Monomer Having a Functional Group and a Polymerizable Carbon-Carbon Double Bond, and Multilayer Articles Therefrom
DE102009001001A1 (de) * 2009-02-19 2010-09-02 Evonik Degussa Gmbh Verwendung eines Leitungsrohrs zur Herstellung einer im Wasser verlegten Rohrleitung
DE102010003909A1 (de) * 2010-04-13 2011-10-13 Evonik Degussa Gmbh Flexibles Rohr mit mehrschichtigem Aufbau
JP5607442B2 (ja) * 2010-07-09 2014-10-15 スリーエム イノベイティブ プロパティズ カンパニー フルオロポリマー系粘接着性組成物
DE202010018527U1 (de) * 2010-08-13 2017-05-29 Ebm-Papst Landshut Gmbh Mischvorrichtung zur Mischung von Verbrennungsluft und Gas sowie Feuerungseinrichtung
WO2012057237A1 (ja) * 2010-10-27 2012-05-03 ダイキン工業株式会社 積層体
GB201108963D0 (en) * 2011-05-27 2011-07-13 3M Innovative Properties Co Composite materials comprising polyamides and fluoroelastomers
JP2013064423A (ja) * 2011-09-15 2013-04-11 Tokai Rubber Ind Ltd 燃料ホース
JP5963162B2 (ja) * 2012-01-30 2016-08-03 住友理工株式会社 樹脂ホースおよびその製法
JP5505484B2 (ja) * 2012-10-22 2014-05-28 Ｎｏｋ株式会社 樹脂ゴム複合体
US9995416B2 (en) 2012-10-25 2018-06-12 Ge Oil & Gas Uk Limited Flexible pipe body layer and method of producing same
JP6137667B2 (ja) * 2013-01-25 2017-05-31 本田技研工業株式会社 自動二輪車用燃料供給装置
US10197207B2 (en) * 2015-01-22 2019-02-05 Hamilton Sundstrand Corporation Conductive elastomeric flexible coupling
US20180358492A1 (en) * 2015-12-10 2018-12-13 Panasonic Intellectual Property Management Co. Ltd. Solar cell module
CN110198840B (zh) * 2017-11-20 2021-06-25 住友电工超效能高分子股份有限公司 耐热双层热收缩管和用于覆盖待覆盖的物体的方法
JP7382149B2 (ja) * 2019-03-19 2023-11-16 住友理工株式会社 多層チューブ
WO2020204079A1 (ja) * 2019-04-04 2020-10-08 Ａｇｃ株式会社 積層体の製造方法および積層体
CN110330745B (zh) * 2019-07-10 2022-03-04 陕西奉航科技有限责任公司 一种汽车用粘接式ptfe油封的制备方法
EP4441409A1 (de) 2021-12-02 2024-10-09 Omega Flex, Inc. Lichtbogenbeständige wellrohre mit schutzmantel und anschlussstück
US11994241B2 (en) 2021-12-02 2024-05-28 Omega Flex, Inc. Arc resistant corrugated tubing system with protective jacket and fitting

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4308363A (en) * 1980-04-03 1981-12-29 The Dow Chemical Company Halogenation of organic polymers having anhydride groups
US4318881A (en) * 1980-05-19 1982-03-09 Raychem Corporation Method for annealing PTC compositions
JPS5859275A (ja) * 1981-10-05 1983-04-08 Daikin Ind Ltd 耐潤滑油性シ−ル材
JPS6012791U (ja) * 1983-07-06 1985-01-28 東海ゴム工業株式会社 ホ−スと接続管の接続構造
JPS60113882A (ja) * 1983-11-22 1985-06-20 株式会社ブリヂストン ゴム管状物
JPS63112686U (de) * 1987-01-13 1988-07-20
US4863788A (en) * 1988-02-16 1989-09-05 Micropore Waterproof breathable microporous membrane with cellular foam adhesive
JPH0671735A (ja) * 1992-08-28 1994-03-15 Tokai Rubber Ind Ltd ホースの製造方法
MX9606273A (es) * 1994-06-17 1998-03-31 Allied Signal Inc Articulos de manufactura que comprende mezclas extruidas de injertos de poliamida y polietileno de baja densidad.
US5552199A (en) * 1994-09-02 1996-09-03 Minnesota Mining And Manufacturing Company Melt-processable electroconductive fluoroplastic
JPH09117977A (ja) * 1995-10-25 1997-05-06 Mitsubishi Chem Corp 多層樹脂製燃料タンク
JP3261969B2 (ja) * 1996-02-29 2002-03-04 豊田合成株式会社 ホースとその製造方法
JPH10311461A (ja) * 1997-05-12 1998-11-24 Asahi Glass Co Ltd 燃料ホース
US6372870B1 (en) * 1997-06-23 2002-04-16 Daikin Industries Ltd. Tetrafluoroethylene copolymer and use thereof
JP3695092B2 (ja) * 1997-10-16 2005-09-14 豊田合成株式会社 燃料ホース
JPH11207840A (ja) * 1998-01-28 1999-08-03 Mitsubishi Chemical Corp 多層管状体
JP3905225B2 (ja) * 1998-06-29 2007-04-18 東海ゴム工業株式会社 二酸化炭素冷媒輸送用ホース
US6221626B1 (en) * 1998-06-30 2001-04-24 University Of Geneva Kit for electroblotting polypeptides separated on an electrophoresis gel
JP2000015754A (ja) * 1998-07-07 2000-01-18 Mitsubishi Chemicals Corp 樹脂積層体
JP2000052446A (ja) * 1998-08-10 2000-02-22 Tokai Rubber Ind Ltd 燃料ホースの製法およびそれによって得られた燃料ホース

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0165161A1 *

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1450092A1 (de) * 2003-02-24 2004-08-25 MANIFATTURA TUBI GOMMA S.p.A. Flüssigkeitsführendes Rohr und Verfahren zu seiner Herstellung
EP1484346A1 (de) * 2003-06-06 2004-12-08 Atofina Verfahren zur Pfropfung von Fluorpolymeren und Schichtverbundmaterial daraus
FR2856404A1 (fr) * 2003-06-06 2004-12-24 Atofina Procede de greffage de polymere fluore et structures multicouches comprenant ce polymere greffe
FR2856403A1 (fr) * 2003-06-06 2004-12-24 Atofina Procede de greffage de polymere fluore et structures multicouches comprenant ce polymere greffe
SG118270A1 (en) * 2003-06-06 2006-01-27 Atofina Process for grafting a fluoropolymer and multilayer structures comprising this grafted polymer
US7472723B2 (en) 2004-03-17 2009-01-06 Manifattura Tubi Gomma S.P.A. Tube for conveying fluids and method for its production
EP1580474A1 (de) * 2004-03-25 2005-09-28 MANIFATTURA TUBI GOMMA S.p.A. Mehrschichtiger, flexibler Schlauch
WO2006097678A1 (en) * 2005-03-14 2006-09-21 Wellstream International Limited Pipe fitting
EP1897685A4 (de) * 2005-06-14 2010-10-27 Asahi Glass Co Ltd Mehrschichtiges fluorharzlaminat
WO2007021782A1 (en) * 2005-08-12 2007-02-22 E. I. Du Pont De Nemours And Company Multilayered pipes
EP2409830A1 (de) * 2006-01-20 2012-01-25 Arkema France Polyamidschlauch für Druckluft
WO2007083041A3 (fr) * 2006-01-20 2007-10-18 Arkema France Tuyau flexible en polyamide pour l’air comprime
EP2101095A3 (de) * 2008-03-12 2013-07-17 Rehau AG + Co Wellschlauch aus Kunststoffmaterial zur Ummantelung von wenigstens einem Abgassensor-Kabel
US8627713B2 (en) 2008-09-08 2014-01-14 Arkema France Method for predetermining the fatigue life of polymer composition
WO2012017265A1 (en) * 2010-08-02 2012-02-09 Intertechnique Tube with protrusions for inflatable harness of breathing mask
CN103108676A (zh) * 2010-08-02 2013-05-15 联合技术公司 用于呼吸面罩的充气安全带的带有突出物的管子
WO2012028948A3 (en) * 2010-09-03 2012-04-26 Aerazur S.A. Thermoplastic hoses for airborne vehicles
EP2918885A1 (de) * 2014-03-14 2015-09-16 Veritas Ag Schlauchleitung für ein fluid
US9506584B2 (en) 2014-03-14 2016-11-29 Veritas Ag Hose line for a fluid
CN106051330A (zh) * 2016-07-21 2016-10-26 中山市庆谊金属制品企业有限公司 一种新型水管
WO2020120523A1 (de) 2018-12-12 2020-06-18 Ems-Patent Ag Mehrschicht-kraftstoffleitung
US12392426B2 (en) 2018-12-12 2025-08-19 Ems-Chemie Ag Multilayer fuel line
EP3882316A1 (de) * 2020-03-20 2021-09-22 ContiTech Techno-Chemie GmbH Umlageschlauch mit einem fkm-coating

Also Published As

Publication number Publication date
WO2001065161A1 (en) 2001-09-07
CN1226544C (zh) 2005-11-09
US20030099799A1 (en) 2003-05-29
CN1418302A (zh) 2003-05-14
AU2001236043A1 (en) 2001-09-12

Similar Documents

Publication Publication Date Title
EP1260747A1 (de) Kunststoffschlauch für kraftstoff
EP1313613B1 (de) Mehrschichtartikel welche eine fluorkunststoffschicht enthalten
CN100540292C (zh) 包括含氟弹性体层和阻挡层的多层制件及其制造方法
JP2578705B2 (ja) 燃料配管用樹脂チューブ及びその製造法
JP4780153B2 (ja) 積層樹脂成形体、積層樹脂成形体製造方法及び多層成形品
JP5482790B2 (ja) 積層体
US6524671B1 (en) Coextruded fluoropolymer/polyamide laminate
US20030124288A1 (en) Polyamide- and EVOH-based conducting multilayer tube for transporting petrol
EP1160496A1 (de) Kraftstoffschlauch
WO2002016112A1 (en) Process for preparing a multi-layer article having a fluoroplastic layer and an elastomer layer
JP6966711B2 (ja) 積層体
US20070036926A1 (en) Multilayered pipes
US20030113464A1 (en) Process for preparing a multi-layer article having a fluoroplastic layer and an elastomer layer
JP2002210892A (ja) 接着積層体及び燃料ホース
JPWO2001065161A1 (ja) 燃料用樹脂ホース
JP4170395B2 (ja) 共押出積層品
JPH0825578A (ja) 積層構造ホース
JPH09196248A (ja) 燃料ホース

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20020903

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

RBV Designated contracting states (corrected)

Designated state(s): DE FR GB

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20090122